CN113316664B - 合金涂覆钢板及其制造方法 - Google Patents

合金涂覆钢板及其制造方法 Download PDF

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Publication number
CN113316664B
CN113316664B CN201980089726.8A CN201980089726A CN113316664B CN 113316664 B CN113316664 B CN 113316664B CN 201980089726 A CN201980089726 A CN 201980089726A CN 113316664 B CN113316664 B CN 113316664B
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steel sheet
alloy
layer
coating
coated steel
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CN113316664A (zh
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梁智勋
郑在仁
李庚晃
郑勇华
金兑烨
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Research Institute of Industrial Science and Technology RIST
Posco Holdings Inc
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Posco Co Ltd
Research Institute of Industrial Science and Technology RIST
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/14—Metallic material, boron or silicon
    • C23C14/16—Metallic material, boron or silicon on metallic substrates or on substrates of boron or silicon
    • C23C14/165—Metallic material, boron or silicon on metallic substrates or on substrates of boron or silicon by cathodic sputtering
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/02—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings only including layers of metallic material
    • C23C28/021—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings only including layers of metallic material including at least one metal alloy layer
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
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    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
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    • B32B15/01—Layered products comprising a layer of metal all layers being exclusively metallic
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B32B15/00—Layered products comprising a layer of metal
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    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B32B15/18—Layered products comprising a layer of metal comprising iron or steel
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D9/00—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor
    • C21D9/46—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor for sheet metals
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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    • C22C18/04—Alloys based on zinc with aluminium as the next major constituent
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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    • C22C21/06—Alloys based on aluminium with magnesium as the next major constituent
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    • C22C—ALLOYS
    • C22C21/00—Alloys based on aluminium
    • C22C21/10—Alloys based on aluminium with zinc as the next major constituent
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C30/00—Alloys containing less than 50% by weight of each constituent
    • C22C30/06—Alloys containing less than 50% by weight of each constituent containing zinc
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
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    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
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    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
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Abstract

本发明公开一种合金涂覆钢板，其包含：钢板；以及Al‑Mg‑Si‑Zn合金层，其位于所述钢板上，所述Al‑Mg‑Si‑Zn合金层包含Mg‑Zn合金相，所述Mg‑Zn合金相包含MgZn2和Mg2Zn11，还包含MgZn、Mg21Zn25、Mg51Zn20和Mg2Zn3中的一种以上。

Description

合金涂覆钢板及其制造方法
技术领域
本发明涉及一种合金涂覆钢板及其制造方法。更具体地，本发明涉及一种可提高耐腐蚀性和牺牲防腐蚀性的合金涂覆钢板及其制造方法。
背景技术
铁是一种资源丰富以及性能优良的金属，因此工业上使用最多。尽管有许多优点，但是铁的缺点在于，它与氧气或水发生电化学反应引起铁离子溶出的腐蚀，从而导致性能下降。铁的腐蚀所产生的铁锈由各种化学计量的氧化物和氢氧化物组成，随着时间的推移不断发生氧化，这是铁的特性之一。铁加工成各种形式以供使用，对于汽车或建筑材料、家电产品，主要使用冷轧的钢板，即冷轧钢板。
用于防止钢板腐蚀的典型方法是在钢板表面镀上另一种金属。镀膜类型可分为牺牲防腐蚀型膜层和阻隔防腐蚀型膜层。牺牲防腐蚀型膜层中包覆有比铁更容易氧化以及容易生锈的金属如锌或镁、铝等，被包覆的金属优先腐蚀，从而保护钢板。阻隔防腐蚀型膜层是用铅或锡等非腐蚀性金属来包覆铁，以阻隔水和氧气避免其到达铁层。
目前，最广泛使用的用于防止钢板腐蚀的方法是镀锌。自从开发出镀锌钢板以来，已经做出各种努力以提高耐腐蚀性，其中之一是包覆锌合金。利用合金的高耐腐蚀性材料体系有Zn-Al、Zn-Ni、Zn-Fe、Zn-Al-Mg等。这种锌或锌合金镀层钢板广泛用于汽车、建筑材料和家电产品。
铝也用于防止钢板腐蚀，但是不同于锌，铝的应用领域更广。铝膜色泽艳丽，具有优良的耐腐蚀性和耐热性，因此不仅用作化妆品盒或配饰等的装饰膜，还用于半导体的导电膜、磁性材料或钢板的保护膜、温热系统的家电产品、汽车消声器。
铝膜采用真空涂覆、电镀或热浸镀法制成。然而，在电镀的情况下，由于效率低，生产率下降，所以多采用热浸镀法和真空涂覆法。
镀铝钢板具有优良的耐腐蚀性，但是存在膜层中产生缺陷时腐蚀集中在该缺陷部位的缺点，这是因为铝的牺牲防腐蚀性低于锌。因此，对于热浸镀铝钢板，通过将厚度增加到15μm以上来克服上述的缺点。热浸镀铝钢板也是在高温下完成工艺，因此存在界面处形成Al-Fe合金导致加工性下降的缺点。
采用真空涂覆的铝膜在大多数应用中厚度都较薄，在耐腐蚀性涂覆中通常也涂覆成几微米的厚度。
对于铝膜，当厚度为几微米以下时，在盐雾试验中大约72小时就会出现红锈。因此，为了将铝作为耐腐蚀性涂层应用到钢板上，必须提高性能。此外，由于牺牲防腐蚀特性低于锌，一旦发生红锈，就会在短时间内蔓延到整个表面。因此，迫切需要进行研究，以解决上述的问题。
发明内容
(一)要解决的技术问题
本发明提供一种可提高耐腐蚀性和牺牲防腐蚀性的合金涂覆钢板及其制造方法。
(二)技术方案
根据本发明的一个实施例的合金涂覆钢板，其包含：钢板；以及Al-Mg-Si-Zn合金层，其位于所述钢板上，所述Al-Mg-Si-Zn合金层包含Mg-Zn合金相，所述Mg-Zn合金相包含MgZn2和Mg2Zn11，还包含MgZn、Mg21Zn25、Mg51Zn20和Mg2Zn3中的一种以上。
所述Al-Mg-Si-Zn合金层还可包含Al-Mg合金相和Mg-Si合金相中的一种以上。
相对于总量100重量％，所述Al-Mg-Si-Zn合金层可包含1至45重量％的Zn。
相对于总量100重量％，所述Al-Mg-Si-Zn合金层可包含5至30重量％的Mg。
所述Al-Mg-Si-Zn合金层还可包含Al-Mg合金相和Mg-Si合金相中的一种以上。
所述Al-Mg合金相可包含Al3Mg2和Al12Mg17中的一种以上。
所述Mg-Si合金相可包含Mg2Si。
所述合金涂覆钢板还可包含Al-Fe-Si合金层，其位于所述钢板和所述Al-Mg-Si-Zn合金层之间。
根据本发明的一个实施例的合金涂覆钢板的制造方法，其包含：准备步骤，准备形成有含Al和Si的镀层的镀覆钢板；第一涂覆步骤，在所述镀层上形成含Mg的Mg涂层；第二涂覆步骤，在所述Mg涂层上形成含Zn的Zn涂层；以及热处理步骤，对形成有所述Mg涂层和Zn涂层的镀覆钢板进行热处理，以使所述Mg和所述Zn扩散到所述镀层。
在所述准备步骤中，所述镀覆钢板可为热浸镀铝钢板。
在所述第一涂覆步骤和所述第二涂覆步骤中，可以利用物理气相沉积(PVD)来形成所述Mg涂层和所述Zn涂层。
在所述热处理步骤中，可以以300至450℃的温度进行热处理。
在所述热处理步骤中，可以热处理5至600秒。
(三)有益效果
根据本发明的一个实施例的合金涂覆钢板及其制造方法，通过形成包含Mg-Zn合金相的Al-Mg-Si-Zn合金层，可以提高耐腐蚀性和牺牲防腐蚀性。
附图说明
图1是可用于制造合金涂覆钢板的连续涂覆装置的示意图。
图2是根据本发明的一个实施例的合金涂覆钢板的截面示意图。
图3是根据本发明的一个实施例的合金涂覆钢板的辉光放电光谱分析结果。图3的(a)是Zn含量为1.2重量％，图3的(b)是Zn含量为2.6重量％，图3的(c)是Zn含量为7.9重量％的涂覆钢板的辉光放电光谱分析结果。
图4是根据本发明的一个实施例的合金涂覆钢板的X射线衍射分析结果。
图5是本发明的实施例1和比较例1的合金涂覆钢板的盐雾试验结果。
具体实施方式
第一、第二、第三等词汇用于描述各部分、成分、区域、层和/或段，但这些部分、成分、区域、层和/或段不应该被这些词汇限制。这些词汇仅用于区分某一部分、成分、区域、层和/或段与另一部分、成分、区域、层和/或段。因此，在不脱离本发明的范围内，下面描述的第一部分、成分、区域、层和/或段也可以被描述为第二部分、成分、区域、层和/或段。
本文所使用的术语只是出于描述特定实施例，并不意在限制本发明。除非上下文中另给出明显相反的含义，否则本文所使用的单数形式也意在包含复数形式。在说明书中使用的“包含”可以具体指某一特性、领域、整数、步骤、动作、要素和/或成分，但并不排除其他特性、领域、整数、步骤、动作、要素、成分和/或组的存在或附加。
如果某一部分被描述为在另一个部分之上，则可以直接在另一个部分上面或者其间存在其他部分。当某一部分被描述为直接在另一个部分上面时，其间不存在其他部分。
虽然没有另作定义，但是本文中使用的所有术语(包含技术术语和科学术语)的含义与本发明所属领域的普通技术人员通常理解的意思相同。
对于辞典中定义的术语，应该被解释为具有与相关技术文献和本文中公开的内容一致的意思，而不应该以理想化或过于正式的含义来解释它们的意思。
在下文中，将详细描述本发明的实施例，以使本发明所属领域的普通技术人员容易实施本发明。然而，本发明能够以各种不同方式实施，并不限于本文所述的实施例。
近来，为了解决热浸镀铝钢板所具有的问题，正在研究通过含硅的热浸镀铝钢板中加入镁来提高耐腐蚀性和牺牲防腐蚀性。
作为一个实例，正在研究通过热浸镀制造Al-Mg-Si镀覆钢板以制造耐腐蚀性优良的涂覆钢板。然而，当通过热浸镀方式制造时，Mg含量控制上存在限制，当采用20g/m2以下的薄镀时，存在耐腐蚀性迅速降低的问题。此外，已知Mg2Si合金相起到提高耐腐蚀性的作用，但是在此情况下，只有在Mg约6％的较窄范围内提高特性。
已知Al-Mg-Si镀覆钢板具有优良的耐腐蚀性，因为镀层中形成有Mg2Si相。据报道，镀层中以面积比Mg2Si相为0.5％以上且30％以下和Mg2Si相的长径为10μm以下时提高Al-Mg-Si镀覆钢板的耐腐蚀性。然而，对于通过热浸镀方法制作的Al-Mg-Si镀覆钢板，在制作工艺上Mg含量控制受到限制，因此不易制作具有一定含量以上的Mg含量(约15％以上)的Al-Mg-Si镀覆钢板。由于Al-Mg-Si镀覆钢板的Mg含量限制和较高的工艺温度，Al-Mg-Si合金层中难以形成金属间化合物Mg2Si相之外的Al3Mg2相或Al12Mg17相。
作为另一个实例，正在研究关于将涂覆铝的基板在真空中以350℃以上且500℃以下的温度加热的状态下沉积Mg以形成Al-Mg合金层的方法和热浸镀铝钢板上以物理气相沉积涂覆Mg后热处理的方法。然而，这些方法是在真空中将Mg沉积于以高温加热的基板上，因此可能会发生蒸气的损失，而且关于Al-Mg-Si层没有给出金属间化合物的生成或金属间化合物导致的特性变化资料。
为了解决上述的热浸镀铝钢板所具有的问题以及Al-Mg合金钢板的问题，利用物理气相沉积在热浸镀铝钢板上涂覆Mg，并实施扩散热处理，以提高Mg含量以及镀层中形成金属间化合物，从而开发出提高牺牲防腐蚀性的Al-Mg-Si涂覆钢板。所开发的涂覆钢板是通过物理气相沉积将Mg涂覆在热浸镀铝钢板上，因此Al-Mg-Si涂层的Mg含量控制不受限制，可以制作各种涂层结构。在含硅的热浸镀铝钢板上沉积Mg，并通过热处理形成合金膜，从而提供一种合金涂覆钢板，具有牺牲防腐蚀性，同时在薄厚度下也具有高耐腐蚀特性。
本发明提供一种Al-Mg-Si涂覆钢板中加入Zn来提高耐腐蚀性的高耐腐蚀钢板及其制造方法。具体地，通过物理气相沉积在具有含Al和Si的镀层的镀铝钢板上涂覆Mg和Zn，并实施扩散热处理，使得镀层中存在金属间化合物和固溶的Mg和Zn，从而可以提高涂覆钢板的耐腐蚀性和牺牲防腐蚀性。
合金涂覆钢板的制造方法
根据本发明的一个实施例的合金涂覆钢板的制造方法，其包含：准备步骤，准备形成有含Al和Si的镀层的镀覆钢板；第一涂覆步骤，在镀层上形成含Mg的Mg涂层；第二涂覆步骤，在Mg涂层上形成含Zn的Zn涂层；以及热处理步骤，对形成有Mg涂层和Zn涂层的镀覆钢板进行热处理，以使Mg和Zn扩散到镀层。
首先，在准备步骤中，准备形成有含Al和Si的镀层的镀覆钢板。镀覆钢板可为热浸镀铝钢板。具体地，相对于总量100重量％，镀层可包含88至90重量％的Al、8至10重量％的Si和5重量％以下的Fe。
镀层可包含形成在钢板上的Al-Fe-Si合金层和形成在Al-Fe-Si合金层上的Al-Si层。Al-Fe-Si合金层可以是制造镀覆钢板时镀覆钢板的Fe扩散到镀层而形成的合金层。
接下来，在第一涂覆步骤中，在镀层上形成含Mg的Mg涂层。此时，Mg的涂覆可以采用物理气相沉积(PVD)。具体地，可以采用电磁悬浮物理气相沉积(EML-PVD)，但是不限于此，可以采用各种方法涂覆Mg，通过电子束蒸发装置、热蒸发装置、溅射源、阴极电弧源等物理方法沉积Mg即可。
接下来，在第二涂覆步骤中，在Mg涂层上形成含Zn的Zn涂层。此时，Zn的涂覆可以采用物理气相沉积(PVD)。具体地，可以采用电磁悬浮物理气相沉积(EML-PVD)，但是不限于此，可以采用各种方法涂覆Zn，通过电子束蒸发装置、热蒸发装置、溅射源、阴极电弧源等物理方法沉积Zn即可。
接下来，在热处理步骤中，对形成有Mg涂层和Zn涂层的镀覆钢板进行热处理，以使Mg和Zn扩散到镀层。可以利用感应加热装置进行热处理，但是不限于此，可以采用适宜的其他热处理装置。
具体地，可以以300至450℃的温度进行热处理，并且可以热处理5至600秒。
由于通过热处理使Mg和Zn扩散到镀层，热处理后形成Al-Mg-Si-Zn合金层。Al-Mg-Si-Zn合金层包含Mg-Zn合金相，还可包含Al-Mg合金相和Mg-Si合金相中的一种以上。
Mg-Zn合金相包含MgZn2和Mg2Zn11，还包含MgZn、Mg21Zn25、Mg51Zn20和Mg2Zn3中的一种以上。
通过镀覆钢板上沉积Mg涂层和Zn涂层后进行热处理的方式来制造，而不是将钢板浸渍在含Al、Mg、Si和Zn的镀浴中实施热浸镀，因此Mg-Zn合金相中不仅包含稳定的MgZn2和Mg2Zn11，还包含不稳定的相，即MgZn、Mg21Zn25、Mg51Zn20和Mg2Zn3中的一种以上。
除此之外，Al-Mg合金相可包含Al3Mg2和Al12Mg17中的一种以上，Mg-Si合金相可包含Mg2Si。
图1是可用于制造合金涂覆钢板的连续涂覆装置的示意图。然而，这仅仅是根据本发明的一个实施例的示例，本发明不限于此。
图1中公开的装置由大气中供应热浸镀铝钢板17的钢板供应装置11、真空中可以预处理钢板的反磁控溅射源(Inverse Magnetron Source)12、预处理后涂覆Mg和Zn的物理气相沉积(physical vapor deposition：PVD)装置13、以及可对排出到大气中的钢板进行热处理的感应加热装置14、重新卷取热处理后的涂覆钢板的钢板排出装置15组成。
物理气相沉积装置13可以是电磁悬浮(electromagnetic levitation；EML)源。真空容器16内可安装和运行反磁控溅射源12和物理气相沉积装置13。
首先，准备热浸镀铝钢板17，并且可以实施碱脱脂，以去除粘附在镀覆钢板表面上的残油如防锈油。
然后，通过钢板供应装置11输送镀覆钢板，将其供应到真空容器16中。然后，可以向安装在真空容器16内的反磁控溅射源12供电进行镀覆钢板的表面清洁。
清洁完毕后，继续输送镀覆钢板，并通过安装在真空容器16内的电磁悬浮源13，可以将Mg和Zn真空涂覆在镀层上。Mg和Zn涂层可以通过两层形式和同时涂覆来形成。
涂覆完毕后，继续输送镀覆钢板，将其排出到大气中，然后可以在大气中利用感应加热装置14以一定温度和时间进行热处理。热处理完毕后，继续输送钢板，可以获得所制造的合金涂覆钢板。
合金涂覆钢板
参见图2，根据本发明的一个实施例的合金涂覆钢板包含钢板和位于钢板上的Al-Mg-Si-Zn合金层，Al-Mg-Si-Zn合金层包含Mg-Zn合金相，Mg-Zn合金相包含MgZn2和Mg2Zn11，还包含MgZn、Mg21Zn25、Mg51Zn20和Mg2Zn3中的一种以上。
Mg-Zn合金相中不仅包含稳定的MgZn2和Mg2Zn11，还包含较为不稳定的相，即MgZn、Mg21Zn25、Mg51Zn20和Mg2Zn3中的一种以上。这可能是因为通过镀覆钢板上沉积Mg涂层和Zn涂层后进行热处理的方式来制造合金涂覆钢板。由于存在这种Mg-Zn合金相，可以提高涂覆钢板的耐腐蚀性和牺牲防腐蚀性。
除此之外，Al-Mg-Si-Zn合金层还可包含Al-Mg合金相和Mg-Si合金相中的一种以上。Al-Mg合金相可包含Al3Mg2和Al12Mg17中的一种以上，Mg-Si合金相可包含Mg2Si。
相对于总量100重量％，Al-Mg-Si-Zn合金层可包含40至80重量％的Al、15至30重量％的Mg、1至10重量％的Si和1至20重量％的Zn。当Zn含量大于45重量％时，由于Zn过多，Zn-Mg金属间化合物的量增加，可能会发生表面变黑、耐腐蚀性降低等问题。
由于在形成有含Al和Si的镀层的镀覆钢板上形成Mg涂层和Zn涂层后进行热处理，镀覆钢板的Fe部分扩散到镀层，因此Al-Fe-Si合金层可位于钢板和Al-Mg-Si-Zn合金层之间。
除此之外，用上述合金涂覆钢板的制造方法中的描述来替代对合金涂覆钢板的描述。
下面描述本发明的具体实施例。然而，下述实施例只是本发明的一个具体实施例而已，本发明不限于下述实施例。
实施例
(1)制造合金涂覆钢板
[实施例1]采用物理气相沉积(PVD)在形成有含Al和Si的镀层的热浸镀铝钢板上形成Mg涂层和Zn涂层，然后在400℃的热处理温度下实施热处理300秒。以热处理后生成的Al-Mg-Si-Zn合金层为基准，Zn为1.2重量％。
[实施例2]除了Zn为2.6重量％之外，制造条件与实施例1相同。
[实施例3]除了Zn为5.0重量％之外，制造条件与实施例1相同。
[实施例4]除了Zn为8.0重量％之外，制造条件与实施例1相同。
[实施例5]除了Zn为10.0重量％之外，制造条件与实施例1相同。
[实施例6]除了Zn为15.0重量％之外，制造条件与实施例1相同。
[实施例7]除了Zn为42.6重量％之外，制造条件与实施例1相同。
[比较例1]除了在没有形成Zn涂层的情况下实施热处理之外，制造条件与实施例1相同。
(2)观察合金涂覆钢板的微细结构变化
图3是用辉光放电光谱仪分析基于Zn含量的涂层组分的结果。图3的(a)是Zn含量为1.2重量％，图3的(b)是Zn含量为2.6重量％，图3的(c)是Zn含量为7.9重量％的涂覆钢板的辉光放电光谱分析结果。如图3所示，在400℃的热处理温度下实施300秒时，将会发生Mg和Zn的扩散，从而扩散到镀铝层。Mg和Zn的扩散深度为约3μm。
另一方面，图4是基于Zn重量％的X射线衍射分析结果，由图4可知，无论Zn含量如何，都会形成Al-Mg、Mg-Si合金相。在30°以下观察到MgZn、MgZn2、Mg21Zn25等形式的Mg-Zn合金相。随着Zn含量降低，X射线衍射分析结果是Mg-Zn合金相的强度小于Al-Mg合金相和Mg-Si合金相的强度。
(3)评价合金涂覆钢板的耐腐蚀性
图5示出未含有Zn的Al-Mg-Si(比较例1)涂覆钢板和含有1.2重量％的Zn的Al-Mg-Si-Zn涂覆钢板(实施例1)的盐雾试验结果。盐雾试验是按照ASTM B-117实施。
如图5和表1所示，未含有Zn的涂覆钢板在2700小时后红锈扩散到整个试样，而含有1.2重量％的Zn的涂覆钢板在2700小时后红锈也没有扩散到整个试样。实施例3、5、6是4500小时后红锈面积也小于实施例1。实施例7是Zn含量为42.6质量％，在实施例中耐腐蚀性最低。这是因为，如前所述Zn含量变高时金属间化合物增加，从而发生变黑以及耐腐蚀性降低的现象。
【表1】
本发明能以各种不同方式实施，并不局限于上述的实施方案和/或实施例，本发明所属技术领域的普通技术人员可以理解在不改变本发明的技术思想或必要特征的情况下能够通过其他具体方式实施本发明。因此，应该理解上述的实施方案和/或实施例在所有方面都是示例性的，并不是限制性的。

Claims (8)

1.一种合金涂覆钢板，其包含：
钢板；以及
Al-Mg-Si-Zn合金层，其位于所述钢板上，
所述Al-Mg-Si-Zn合金层包含Mg-Zn合金相，
所述Mg-Zn合金相包含MgZn2和Mg2Zn11，还包含MgZn、Mg21Zn25、Mg51Zn20和Mg2Zn3中的一种以上，
其中，相对于总量100重量％，所述Al-Mg-Si-Zn合金层包含40至80重量％的Al、15至30重量％的Mg、1至10重量％的Si和1至20重量％的Zn。
2.根据权利要求1所述的合金涂覆钢板，其中，
所述Al-Mg-Si-Zn合金层还包含Al-Mg合金相和Mg-Si合金相中的一种以上。
3.根据权利要求2所述的合金涂覆钢板，其中，
所述Al-Mg合金相包含Al3Mg2和Al12Mg17中的一种以上。
4.根据权利要求2所述的合金涂覆钢板，其中，
所述Mg-Si合金相包含Mg2Si。
5.根据权利要求1所述的合金涂覆钢板，其还包含：
Al-Fe-Si合金层，其位于所述钢板和所述Al-Mg-Si-Zn合金层之间。
6.一种合金涂覆钢板的制造方法，其包含：
准备步骤，准备形成有含Al和Si的镀层的镀覆钢板；
第一涂覆步骤，在所述镀层上形成含Mg的Mg涂层；
第二涂覆步骤，在所述Mg涂层上形成含Zn的Zn涂层；以及
热处理步骤，对形成有所述Mg涂层和Zn涂层的镀覆钢板进行热处理，以使所述Mg和所述Zn扩散到所述镀层，其中
在所述第一涂覆步骤和所述第二涂覆步骤中，
利用物理气相沉积来形成所述Mg涂层和所述Zn涂层，
在所述热处理步骤中，
以300至450℃的温度对涂覆的钢板进行热处理，
制造的合金涂覆钢板包含Al-Mg-Si-Zn合金层，
其中相对于总量100重量％，所述Al-Mg-Si-Zn合金层包含40至80重量％的Al、15至30重量％的Mg、1至10重量％的Si和1至20重量％的Zn。
7.根据权利要求6所述的合金涂覆钢板的制造方法，其中，
在所述准备步骤中，
所述镀覆钢板为热浸镀铝钢板。
8.根据权利要求6所述的合金涂覆钢板的制造方法，其中，
在所述热处理步骤中，
热处理所述涂覆的钢板5至600秒。
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